Pushing membrane stability boundaries with HybSi pervaporation membranes

Transcription

1 Pushing membrane stability boundaries with HybSi pervaporation membranes H.M. van Veen R. Kreiter D.P. Shanahan M.D.A. Rietkerk M.M.A. van Tuel H.L Castricum (Univ. Twente) J.E. ten Elshof (Univ. Twente) Jaap Vente Presented at NAMS-ICIM 2010 (North American Membrane Society - Int. Conference on Inorganic Membranes 2010),July 17-22, 2010, Washington, D.C., USA ECN-M August 2010

2 Pushing membrane stability boundaries with HybSi pervaporation membranes Henk van Veen, Robert Kreiter, Donough Shanahan, Mariëlle Rietkerk, Marc van Tuel, Hessel Castricum, Andre ten Elshof, Jaap Vente

3 What is pervaporation Selective evaporation via a membrane Much higher energy efficiency than distillation Membrane Feed Permeation Permeate Evaporation Heating 1 kg water from 25 to 100 o C: Evaporation of 1 kg water: 314 kj 2260 kj 2

4 Commercially available pervaporation membranes Polymers - PVA (Sulzer Chemtech) - Polyimide (Vaperma) Ceramics - Zeolite A (Mitsui, Mitsubishi, Inocermic, Zeolite Solutions) - SiO 2 (Pervatech) 3

5 Towards a generally accepted technology Limitations currently perceived by the end-user - Limited stability - High risk option - Predictability has to improve (where is the predictive tool?) - Application window too small Current challenges - Higher application temperatures - Higher resistance against acids and alkalines - Higher stability in aggressive solvents - Larger application window w.r.t. water content - Effective methanol removal - Resistance against condensation 4

6 The answer: HybSi Strategy replace unstable Si O Si bonds in SiO 2 by stable Si C m H n Si bonds Hybrid layer Precursors Methane bridge BTESM Ethane bridge BTESE Methyl terminating group MTES 5

7 Test results 6

8 Long term and high temperature performance BTESE MTES 150 C 3% H 2 O in BuOH Measurement stopped after 1000 days 7

9 High temperature performance BTESE MTES 190 C 3% H 2 O in BuOH Measurement stopped after 35 days 8

10 High temperature performance BTESM Ethanol dehydration 5 or 10% H 2 O in Ethanol Temperature o C 9

11 Acid resistance (HAc in EtOH) Various levels of HAc in EtOH BTESM 70 C 5% H 2 O in EtOH Water content in permeate: >85% 10

12 Long term behaviour in the presence of acid BTESM 70 C 5% H 2 O in EtOH 1 mol% HAc present 11

13 Acid resistance at higher temperature: glycol + HAc BTESM 130 C 5% H 2 O in glycol 1 mol% HAc 12

14 Acid resistance HNO 3 in BuOH BTESE 95 C 5% H 2 O in BuOH Started with wt% HNO 3 13

15 Acid resistance HNO 3 in BuOH BTESE 95 C 5% H 2 O in BuOH Decrease of selectivity 0.5% HNO 3 ph ~2 seems to be OK 14

16 Limitations 1% MSA in BuOH Methylsulfonic acid BTESE 95 C 5% H 2 O in BuOH w% MSA added. 15

17 Long term behaviour in strong solvent BTESE 130 C 8% H 2 O in NMP 16

18 HybSi advantages over commercial products Higher application temperatures C Higher resistance against acids and alkalines - ~ 2 < ph < ~8 Higher stability in aggressive solvents - NMP, MEK Larger application window w.r.t. water content - Measurement up 30% performed Effective methanol removal - Feasibility shown Resistance against condensation - All liquid feed no issue 17

19 Origins of stability - More stable bonds - Higher crack propagation energy - Lower surface diffusion coefficient - Lower solubility 18

20 Moving to the market Commitment from end users - Tests & module sales - Process analyses Interest from OEM - Letters of interests - Active participation Contract with manufacturers - First licence granted to Pervatech - Letters of intent for joined developments with others 19

21 Lab scale testing for the industry Targeted application tests for DSTI partners Bulk Chemicals sector (about to finish) - Sabic IP - Huntsman Technoproject (about to start) - DSTI in collaboration with NL-GUTS - Huntsman - DSM 20

22 Industrial pilot test Consortium: - Trion Partners, Air Products, Sulzer Chemtech, and Deltalinqs 30m 3 of end of pipe fuel from 30-35% to ~2% water 1m 2 membrane area August October 2010 First result promising! 21

23 Acknowledgements Industrial collaborators - Sabic IP - Huntsman - Air Products - DSM - Sulzer Chemtech - Pervatech - Trion partners Knowledge network University of Twente University of Amsterdam TNO Financial support - STW - AgentschapNL - DSTI Membrane Technology Group 22

24 Chem. Commun, 2008, 1103 J. Mater. Chem, 2008, 18, 2150 J. Sol-Gel Sci. Techn, 2008, 48, J. Mem. Sci, 2008, 319, ChemSusChem, 2009, 2, J. Sol-Gel Sci. Techn, 2010, accepted Patent: WO ; WO For more information: